Catalytic composition and process for preparing same



Patented Dec. 29, 1936 PATENT; OFFICE CATALYTIC ooiwrosrrron AND PROCESS ron PREPARING SAME Wilbur A. Lazier, Marshallton, Del., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Original applicationjuly 23, 1930,

Serial No. 470,238. Divided and this application December 31, 1931, Serial No. 584,293

20 Claims.

This invention relates to novel catalyst compositions and processes for preparing the same, and more particularly the invention relates to promoted chromite catalysts which are especially suitable for the carrying out of organic hydrogenation and dehydrogenation reactions.

This case is a division of my copendlng application Serial No. 470,238, filed July 23, 1930 now Patent 1,964,001. It is also a continuation in part of my copending applications Serial No. 285,501, filed June 14, 1928, now Patent 1,857,921, and Serial No. 445,224, filed April 17, 1930.

The rapid development of technically successful processes of synthesizing useful organic compounds from water gas has led to the proposed use of numerous combinations and mixtures of various catalytic metals andmetallic oxides. In generaL'such catalyst compositions as have been suggested have consisted of two or more elements or compounds in the form of intimate physical mixtures, such as those formed by the comecipitation of hydroxides or salts. A typical and widely used catalyst ofthis type is prepared by co-precipitating a mixture of zinc hydroxideand chromium hydroxide with a base, or by mixing chromic acid with an excess of zinc oxide. According to U. S. Patent 1,746,782 issued to me on February 11, 1930, particularly useful catalyst compositions are obtained by igniting at a red heat chromates of various hydrogenating metals to form chromites containing the hydrogenating metal oxide partially combined with chromium sesqui-oxide to form loosely boundbut very refractory compounds of indefinite chemical composition which may be classified under the term chromites.

Anotherconvenient method of preparing these important chromite catalysts consists of heating a double salt of a hydrogenating metal and a nitrogen base, such as ammonia, to its spontaneous decomposition temperature, as disclosed in Patent 1,746,783. For example, basic zinc ammonium chromate when heated to 400 C. undergoes an exothermic gaseous decomposition resulting in a finely divided, powdery, black residue of zinc chromite containing free zinc oxide as well as zincoxide combined with chromium sesqui-oxide. These simple chromite compositions when used alone as catalysts for various organic hydrogenation and dehydrogenation reactions, have been found to be particularly effective. However, so faras I am aware, no mixed or promoted multiple chromite catalysts containing a plurality of chromites of hydrogenating metals have been developed or applied in such tive data showing the improvement effected cal reactions, especially those involving the hydrogenation of unsaturated carbon compounds, the dehydrogenation of oxygenated organic compounds, such as the alcohols and other hydrogenations and dehydrogenations in general. A further object is to provide a promoted catalyst composition comprising a mixture of various hydrogenating metals in the form of their oxides or chromites, said composition having as a whole a catalytic eifect in the various reactions to which it is applied greater than the sum of the effects of its constituent oxides or chromites.

These objects are accomplished by the following invention which, in its general aspects, comprises mixing or intimately associating a small amount of an oxide or chromite of one or more hydrogenating metals whose oxides are readily reducible with a chromite of one or more hydrogenating metals whose oxides are dimcultly reducible. The invention also contemplates various combinations .or mixtures of chromites of difficultly reducible hydrogenating metal oxides and easily reducible hydrogenating metal oxides, in widely varying proportionsof the respective constituents.

In the following examples I have set forth in detail several catalyst compositions prepared in accordance with the principles of my invention, together with methods for their employment in various catalytic reactions, and also comparathrough their use. These examples are presented only for purposes of illustration and are not to be regarded as limitations.

. ExampleI A. cadmium promoted zinc chromite catalyst ,was prepared as follows: 62 grams of cadmium cipitate of mixed ,basio-zinc ammonium chromate and cadmium chromate was filtered and dried. Inorder to convert the chromates to chromites,

the precipitate was heated in a muflie furnace for four hours at about 400 C. A spontaneous disintegration took place with the evolution or considerable heat, ammonia, and oxides oi nitrogen, resulting in about 9.25% loss in weight and leaving behind an almost black, powdery residue containing the oxides of zinc and cadmium partially combined with chromium sesqui-oxide in the form of chromites. -Thechromium was substantially all converted by the heating process from the hexavalent to the trivalent form. In order to give the' promoted catalyst suitable form, it was compressed into tablets which were broken up and the grains screened to 6-14 mesh.

The activity. or the above described catalyst was tested by. employing it in the catalytic dehydrogenation oi ethyl alcohol vapor at atmospheric pressure as follows: One cc. of the catalyst was placed in a glass reaction tube having a diameter oi 15 mm. in such a manner as to form a disc shaped catalytic. screen held in place with plugs of glass wool. The tube was heated at 400 C. and absolute ethanol vaporwas passed therethrough at the rate oi 50 cc. oi liquid alcohol per hour- There-was formed per hour liters of gas measured at ordinary conditions 01 temperature and pressure, consisting 015% ethylene and 95% hydrogen, representing a conversion of 1% oi .the' alcohol to ethylene and water and.

19.7% to acetaldehyde and hydrogen, or an overall conversion of; about 20.7%.,

By way 01" showing the improvement to be"ob- 'tained by .the addition of a small amount oi cadmium to the above catalyst composition, a plain zinc chromite catalyst prepared by the method described, but .without the use of cadmium, when employed in the same manner in the'same testing equipment, gave only 8.5 liters of gas having 1 the same composition'as indicated above, representing a total conversion 0! the alcohol oi only about 16%. It will be seen. therefore, that the addition 01 cadmium to the zinc chromite catalyst caused a 29% improvement in activity toward this particular reaction.

Example 2 just described was'employed for the catalytic synthesis oi methanol from water gas containing .hydrogen,34% carbon monoxide, 1.5%

bon dioxide and 7% o! methane-and nitrogen.

. A portion oi the catalyst, was'placed in a pressure resisting tube and heated to 352 C. At this ternperature the water gas was through the tube at the rate oi 20,000 volumes or gas. meas-' ured at ordinary conditions or temperature and.

pressure, per unit volume 01 catalyst per hour and at a pressure of 267 atmospheres. There was formed per .100 cc; of catalyst per hour 138 cc. of I crude condensate containing pure methanol.

from the liquid components and The improvement in activity due to the presence of the copper is shown by the fact that a plain zinc chromite catalyst prepared exactly as just described, but without the addition of copper, when employed in methonal synthesis under similar conditions of temperature, pressure, and gas composition, gave per cc. of catalyst per hour only 114 cc. of crude condensate containing 86% methanol.

- Example 3 A special study was made of the eifect of cadmium,-lead, and bismuth when incorporated separately into zinc chromite catalysts employed for the high pressure dehydrogenation of ethanol, wherein ethyl acetate is formed as the major product of the reaction.

The plain zinc chromite control catalyst and- I the three promoted zinc chromites containing the various metals Just mentioned were all made in the same manner by precipitating -2-molar solu- -tions of the base metal salts with an "equivalent amount of B-mola'r neutral ammonium chromate solutions, followed by neutralization with ammonia, washing by decantatiom'flltering, drying and igniting at 400 C.

The plain zinc chromite catalyst was prepared from zinc sulphate. The cadmium-zinc chromite composition was prepared from a solution containing 25 mole per cent cadmium nitrate and 75 mole per cent zinc sulphate. The lead-zinc chromite combination was prepared from a solu- 'iution containing 10 mole per cent lead nitrate and 90 mole per cent zinc nitrate The bismuthzinc chromite catalyst was prepared from a solution containing 10 mole per cent bismuth nitrate and 90 mole per cent zinc nitrate.

Test runs on each of the four catalysts were carried out as follows: 25 cc. of-the catalyst undergoing investigation was loaded into a 5i" cylindrical catalyst bed contained in 'a pressure resisting shell. Ninety-five per cent ethyl alcohol was vaporized and passed over the catalyst at a temperature oi 400 C. and a pressure 01"204 atmospheres, at the rate of 400 cc. of liquid alcohol perhour. The gaseous products were separated the latter analyzed for ethyl acetate.

Disregarding such minor products as aoetaldehyd'e, acetone, butanol, crotonyl alcohol, andestei's higher in molecular weight than ethyl acetate, the following table shows' thelrelative -activities "oi the various catalysts-as measured'by the ester content of thecondensatecalculated as weight per cent of alcohol converted to ethyl acetate:

7 PM mm mm" to St! Zinc chromite (control). ll. Cadmium and zinc 15. Lead and zinc chromite... ll. Bismuth and zinc chromite p i4.

7 His is be notedthat with ash of the catalysts containing as a promoter a hydrogenating metal having a reducible oxide. the yield oi ester is substantislly greater than with zinc chromite alone.

Maximumconversionoiethanoitoethyiaw' tate by high pressure dehydrogenation was obtained when a zinc chromite. catalyst promoted with both copper and cadmium was employed in so elongated reaction tube heated by means ofa temperature.

The catalyst was emptied :by precipitating a. mixed solution containing 82.5 mole per cent of nine sulphate, 'lOmoleperce'nt copper "sulphate and 7.5 mole per cent-cadmium nitrate with a chemically equivalent 'amount of ammonium chromate freshly'prepared from chromic acid and ammonia. The multiple chromates, 'containing also ammoniumchromate, were washed, dried, and ignited at 400", C. to form a black powder containing the chromium oxide stilljuncon bined with the base metals; but existing substantially in the trivalent i'orm. This chronrite material was briquetted, 'crushed'. and screened ta l i-1i;

mesh material.

Twenty-five cc. of the finely grained catalyst was loaded into a cylindrical cartridge which was placed in a vapor heated pressure resisting jacket. in Example 3," 'ethyl alc'ohol, was

pumped therethrough at therate or 400cc. per

" hour; The catalyst temperature wasma'intained at- 380 C. and the pressure jat 204 atmospheres. The liquid condensate contained esters equivalent to aconversion to ethyl acetate of 25 weight per .cent of the alcohol injected. In addition, the condensate contained alittle-acetaldehyde and acetone and 5.8% of material boiling above That the improvement obtained is not the average of the catalytic effects of the various con-' stituent chromites of the composition. as would be expected from a consideration of the eflects of the individual components when acting separately, is shown by the following table in which the conversions of the respective single chromites are given. It is also shown that no two-component chromite catalysts containing 10 mole per cent of the promoting chromites were equal in activity tofthe preferred three-component chromite catalyst of the above example. The tests, were made in the same equipment and under the;

same conditions outlined above, and the catalysts were prepared by the same general method already descrlbed.

Per cent Catalyst Cadmium chromite- Copper chromite Example '5' l lickel and zinc ammoniumlchromates were prepared-by dissolving 29"! grams of zinc nitrate and 290 grams of nickel nitrate in 2.0 liters of water, adding a solution of 250 grams of ammonium bichromate and 350 cc. of ammonium hydroxide'in two liters of water'and heating to boiling. The resulting precipitate was washed, filtered, dried and heated to its spontaneous deilvapdi' hath i a eent w lee compositiontemperaturefiafter which the. result ing' black residue was reduced in hydrogen at 300-475 C. The finalx composition contained 13% elementary nickel. v. i

" when: used 4 i phase hydrogenati n, 10 grams catalyst e the pid ebserw tion" oi hydrogen by a solution er; 100i of glucose in 1100 ccfiof water at a' temperature oi tol was formed quantitatively; I Example 0 a C. andjat a pressure of 1000 Sorbi- A rogenation {catalyst is preparedas ifoilows'z' 2 grams of cadmium nitrate. 24.grams of copper nitrate, and 245 grams of zinc' nitr ate aredissolved in 500 cc. of water andmixd at ordinary temperature with an equalvolumeoi water containing 126 ;-gra ms of. ammonium bichromate-and 751cc. of 28% ammonium hydroxide. After stirring}? the mixture is exactly "neue tralized with additional ammonium hydroxide andallowed to settle. After several washes 'by ,decantation. 'theprecipitate isfdrie'd, ignited at .400 C. and compressed into tablets or grains suitable for use-in catalytic gas apparatus.

Twenty-five cc; of the mixed chromite. catalyst preparedas above was loaded into an'alloy steel reactionvessel capable of being heated and withstanding high pressures. The tube was fitted with a preheater, a'pu'mp for injecting liquid at a constant rate, a T connection for introducing hydrogen under pressure, a suitable condenser,

and trap for separating liquid products, and exit control valves. o A sample of 93% n-butyln-butyrate was subjected to hydrogenation over the catalyst prepared as just indicated. The rate of flow was 700 cc. of ester per 100cc. of catalyst per hour. The system was heated to 346 C. and maintained ata pressure of 2600-3600 pounds- The hydrogenester molecular ratio was 13.8. From 710 cc. of

the butyrate so treated there was obtained by V distillation 580 cc. of pure normal butanol boiling at 117 C., representing a conversionof. the ester to butanol of approximately 73% or the theoretical.

Although in the above examples I have indicated certain definite conditions of temperature,

pressure, gas velocity, amounts of materials, du-' ration of reactions. etc., it is to be understood that any and all of these may be varied widely within the scope of ,my invention, since the particular conditions of operation are governed largely'by the specific reaction, the materials treated, and the catalyst composition selected for a given reaction. o

,The promoted chromite catalysts. which are the subject of this invention, maybe prepared by various methods." For exam le, they may be prepared by heating a mixture of compounds containing one or more hydrogenating metals whose oxides are reducible by hydrogen, one

or more hydrogenatingmetals whose oxides are difliculty reducible or non-reducible by hydrogen and hexavalent chromium, to a temperature sufficient to causethe chromium to be reduced sub- I stantially to the trivalent form. v i

I may, for example, prepare a mixture of copper chromate and zinc chromate and ignite the mixture at a red heat, thatis to say,a temperature of 600 C. or above. in order; to drive oxygen and iorma mixture of copper oxide, zinc oxide, copper chromite and zinc chromite. A.

more convenient method consists of co-precipitoting multiple chromates of the reducible and oxides with;

whereby double ammonium chromates are forms which decompose and callywhen heated toabout m? Br'hsd mtins m ta s I'referto those metals andoxides which are ca'pableiunder proper conditions of serving a'scatalysts for the addition of hydrogento pounds as'ketones or oleflns or arecapable of inducing the hydrogenation of alcohols in the vapor phase in preference to dehydration."

.By difncultly reducible oxides. ,I refer to those which remain substantially in the oxide form after several hours exposure in a pure state to the action of hydrogen at 400 C. Reducible oxides underthesame conditionsare'readlly converted to the elementary metaland water vapor. Suitable h'ydrogenating metals arereadily reducible are silver. copper, cadmium. lead, mercury, tin, bismuth, indium',iron. cobalt and nickel. Hydrogenating metals whoa oxides magnesium, zinc and tain organic compounds. Asindicatedelsewhere,

the eflect ofsuchaddition in the casefof the compositions forming the subject matter of this invention is to give the resulting composition a catalytic effect which is considerably greater than the sumof the eii'ects of the various constituents.

In other words, the catalytic eil'ect ofthe catalyst is not merely the additive effect of thesecompo According to the. principles of my invention, a singlemetal having an easily reducible oxide may be used in conJunctlon with the simple chromites, ora plurality of' such metals may be employed. Among those mentioned above, copper;

and cadmium are particularly useful, either when used alone or in combination. I have found that especially good results are obtained when a copper-cadmium-zinc chromite combination is employed; y

The amount of promoter may be varied within wide limits. In general, I prefer to use'muchless reducible metal oxide than catalytic non-reducible oxide. Suitable concentrations are found between 1 and 25 mole'per cent of the total base metal used. It isto be understood. however, that reducible oxides are not nearly so susceptible" to reduction when combined wholly or in with chromiumoxide toform chromltes as they are when not so. combined, For ,example. a.zinc

chromite catalyst promoted with copper-may be rather'inert to reduction after which .the copper is still contained largely in the oxide form.

The promoted chromite catalyst compositions which are the subject of'this inventionv may be characterized as-flnely divided, refractory, dark colored powders containing chromium sesquioxide rather completely combined with a greater proportion of ahydrogenating metal whose oxide is dlfllcultly reducible and a lesser proportion of a promoting hydrogen'ating metal whose oxide is easily reducible.

essary to form chromites with the chromium ox- Me. The term chromite ashere used does'llot pr'o vethatintlseee Base metal oxideemay or may not be present in excess of the amount necaccents necessarily refer tca'oompound of dennitechem- 'sinee in :thd

f mmsr widelydifandyet 'n a na mamm.

oxide. l 'or example, sine ones}:- completely soluble in liifli aoetic acid. Likewisa'a m compositions, com- Why oo-llecipitation of line bye droxideandchronuumhydroxideyieldssubstantiallyallptlits linc'oxidetomhl-nacid extrac-' vtion. Onthe otherhand, when ainc chromite containing anexcesaof sine-oxide by-igniting xlnc ammonium chromate wasextracted with dilute aoeticacid. the residual product contained iii, of oxide inthe form oi-an acid resistant chromit'eicompound. The same in observed'with chromites and demonstrates-the chemical nature of 'the product.- The. hydrogenatingmetai may exist,

- for example, eitheriin the metallic form",.or'-as an oxide, or both. relationships of the variouselements' ofthecompos'ition depend toa certain extent upon themethodsof preparation and reduction employed. a l

I have disclosed aboveseveral methods of preparation of promoted chromite catalysts,- includingthe heating totheirspontaneous decomposition temperature ,ofmixtures ofcertain double ammonium chrom'ates of various hydrogenating The promoted chromite catalyst compositions of my invention are applicable to a wide variety of catalytic reactions; butv particularly to those.

involving hydrogenation or dehydrogenation oi. organicor other carbon compounds. They are particularly suitable for the dehydrogenation of alcohols a't ordinary-or higher pressures, the catalytic hydrogenation of estersunder pressure to form the corresponding alcohols. thesynthesis of methanol and. higher alcohols from oxides of carbon and hydrogen, the hydrogenation of side.- hydes or ketones under pressure, and the conversion of carbon monoxide and steam to carbon dioxide and hydrogen (the water gas reaction)- As many apparently and 'widelyfdiil'erent embodiments of this invention may be made without departing from the spirit and scope thereof, it

is to be understood that I do not limit myself to the specific embodiments thereof except as defined in the appendedclaims.

I claim:

\ l; A process of forming a catalyst composition 1 which comprises precipitating from an aqueous medium with a chromate of a nitrogen base a mixture of metal chromates, at least one of which is a chromate of a hydrogenating metal whose oxide when exposed for several hours in the pure state to the action'of hydrogen at 400 C. will re-' main substantially in the oxide form'and another of which is a chromate of a hydrogenatingmetal whoseoxide when exposed for several hours in the pure state to the action of hydrogen at 400 C. will be reduced substantially to the metal, and converting the said mixture of metal chromates into one containing the corresponding metal chromites. i

2. A processof forming a composition whlchscomprises co-precipitating troman aqueous medium a mixture of double chromates of several hydrogenating 'metalswith a nitrogen a hydrogenating mew-whose oxide when an,

posed for several hours in the gure'fs'tate to the action of hydrogen zit-400 0.- will remain substantially in the oxide tormand another ot which is a double chromate-bf a hydrogenating metal whose oxide when; exposed-"foi several lhours in the pure state to the action or hydrogen at 400: C. will be reduced substantially to themeta i; and converting said mixture oi chromates into one containing the correspondingm'tal chromites,

3. The process in accordance with clain'i-lchab acterized in thatthe'nitrogen base is *ammon'ia. 4.- A process-off forming'a catalyst compositionwhich comprises co-precipitating' from an aqueous medium a mixture of double chromates of ammonia and: several hydrog'nating "metals, at least one of which is a double-chromate ofa hydrogenating metal whose oxide wh'enexposed for several hours in the pure -'s'tateto' the action of hydrogen at 400 C. remain substantially in the oxide form-and another of whichis a doublechromate of *a hydrogenating metal whose oxide when exposed for several hours in the pure state to the action of hydrogen at 400 C. will be reduced substantially to the metal, and heating the said mixture of double ammonium chromates to its spontaneous decomposition temperature, thus converting the'same into a mixture containingthe corresponding metal chromites.

5. A process of forming a catalyst composition which comprises precipitating from an aqueous medium with a chromate of a nitrogen base a mixture of copper and zinc chromates, and converting said mixture into one containing the corresponding metal chromites.

6. A process of forming a catalyst composition which comprises co-precipitating from an aqueous medium a mixture 01' double chromates of ammonia with zinc and copper, and heating said precipitate to its spontaneous decomposition temperature, thus converting the same into a mixture containing the corresponding metal chromites.

7. A process of forming a catalyst composition which comprises precipitating from an aqueous medium with a chromate of a nitrogen base a mixture of zinc and cadmium chromates, and converting said mixture into one containing the corresponding metal chromites.

8. A process of forming a catalyst composition which comprises co-precipitating from an aqueous medium a mixture of double chromates of ammonia with zinc and cadmium, and heating said precipitate to its spontaneous decomposition temperature, thus converting the same into a mixture containing the corresponding metal chromites.

, 9. A. process of forming a catalyst composition which comprises'precipitating from an aqueous medium with a chromate of a nitrogen base a mixture of zinc, copper, and cadmium chromates, and converting said mixture into one containing the corresponding metal chromites.

10. A process of forming a catalyst composition which comprises co-precipitating from an aqueous medium a mixture of double chromates of ammonia with zinc, copper, and cadmium, and heating said precipitate to its spontaneous decomposition temperature, thus converting the same into a mixture containing the corresponding metal chromites.

11. A catalyst comprising essentially an intimately associated mixture of hydrogenating metal chromites, said catalyst being obtained by the process which comprises precipitating from ahydrogenating metal whose oxidewhen exposed for several hours inthe pure state to the action of hydrogen at 400"C. willbe reduced'substanatially' to the metal, and converting the said mix corresponding metal chromites.

ture of 'metal chromates into onecontaining the 12, A catalyst comprising essentially an inti- -mately associated mixture of 'hydrogenating metal chromites, 'saidfcatalyst being obtained by theprocess which comprises co-precipitating from fan, aqueous medium a mixture, of double chromatesof several hydrogenating metals with a nitrogen base, at least one of whichisa double, chromate of a hydrogenating metal whose oxide when exposed for several hours in the" pure state to the action of hydrogen at 400 C. will remain substantially in the oxide form and another of which is a double chromate of a hydrogenating metal whose oxide when exposed for several hours in the pure state to the action of hydrogen at 400 C. will be reduced substantially to the metal,

and converting said mixture of chromates into one containing the corresponding metal chromites.

13. A catalyst comprising essentially anlintimately associated mixture of hydrogenating metal chromites, said catalyst being obtained by the process which comprises'precipitating from an aqueous medium with a chromate of ammonia a mixture of metal chromates, at least one of which is a chromate of a hydrogenating metal whose oxide when exposed forseveral hours in the pure state to the action of hydrogen at 400 C. will remain substantially in the oxide form and another of which is a chromate of a hydrogenating metal whose oxide when exposed for several hours in the pure state to the action of hydrogen at 400 C will be reduced substantially to the metal, and converting the said mixture of metal chromates into one containing the corresponding metal chromites.

14. A catalyst comprising essentially an intimately associated mixture of hydrogenating metal chromites, said catalyst being obtained by the process which comprises co-precipitating from an aqueous medium a mixture or double chromates of ammonia and several hydrogenat-' ing metals, at least one of which is a double chromate of a hydrogenating metal whose oxide when exposed for several hours in the pure state to the action of hydrogen at 400 C. will remain substantially in the oxide form and another of which is a double chromate of a hydrogenating metal whose oxide when exposed for several hours in the pure state to the action of hydrogen at 400 C. will be reduced substantially to the metal, and heating the said mixture of double ammonium chromates to its spontaneous decom position temperature, thus converting the same into a mixture containing the corresponding metal chromites.

15. A catalyst comprising essentially an intimately associated mixture of zinc'and copper chmmites', said catalystt-being b'ythe ctr-precipitating from mates I of ammoniawith' sine and copper. and

1 heating and precipitate to it's montaneom -de-,

temperature. thus converting the .and'converting saidmixture into onecontaining the corrupondine'metai chromitcs.

18. A mum comprising essentially, an intimatciy associated mixture of zinc and camium chromites. said catalyst being obtained by the process which comprises co-precipitating from an aqueous mediums mixture of double chromsta oi ammonia-with inc and cadmium, and

mately associatodmixtmot 18. A m comprising an, an intiassociated .mixtun'e oi zinc-and copper compoaitionthus itacata'batcompl'lsing mind- I eatalatbem obwn y the process pncipitating cadmium chromatin; and mixture into one metal 20. A cataiyst'compriaing esacntiaily an intimately associated-mixture 0! line. 999 11. and

cadmium chmmite's. mid catalysthoing obtained. by the wprecipitating from an a-mixture'o! double chromates oi ammonia wan-1m, copper. and cadmium. and P'l'ccipitate to its spontaneous converting the same into a mixturevcontaining the correspondingmctalchmmites. I

Mu tan to. its spontaneous de-- l i. i -l y thus 

